DE2126921C3 - Energy-supplying eutectic mixture suitable for the production of explosives with a low solidification point and its use - Google Patents

Description

The invention relates to below -10 ° C liquid, energy-supplying, Eutectic mixtures of fusible components and their use in explosives.

Gas- and energy-supplying, eutectic mixtures based on ammonium nitrate / urea and compounds such as ammonium sulfamate, thiosulfate, formate, acetal, thiocyanate and hypophosphite, acetamides, propionamides and methylamine nitrate are known. The disadvantage of these known mixtures is that the most of them at temperatures above 0 ⁰ C and a few at temperatures between - 10 solidify ⁰ C and 0 ° C; below -10 ⁰ C all these mixtures are solid. For use in practice, however, it is important that the eutectic mixtures also occur at temperatures below. -10 ° C are still liquid.

An energy-providing, eutectic mixture based on oxygen-releasing salts and combustible compounds has now been found which is characterized by a content of at least 30% by weight, preferably 50 to 70% by weight. of nitrates and / or perchlorates of alkanolamines and a freezing point below - 10 ⁰ C.

It has surprisingly been found that the addition of alkanolamine nitrates or perchlorates the freezing point of eutectic mixtures that consist mainly of oxygen-releasing salts and combustible compounds, very strong is reduced, so that the main disadvantages of the known energy-supplying, eutectic Mixtures can be fixed. Mixtures containing these alkanolamine salts in the stated proportions are liquid down to at least -10 "C.

with suitable compositions, however, they are still at -20 ° C. and even lower temperatures fluid.

Primary, secondary and tertiary alkanolamines are suitable as alkanolamines, the nitrates or perchlorates of which are used according to the invention. Examples include: ethanolamine, 2-aminobutanol, 2-aminoisobutanol, diethanolamine, triethanolamine.
It is also possible to add up to 50% by weight of the

ίο alkanolamine salts through the alkylamine nitrates or -perchlorate without the freezing point rising above -10 ° C. The alkyl groups of these Alkylamine salts can be the same as those of the corresponding alkanolamines, but they can also be different from these. Methylamine nitrate is preferably used.

That as the basis for the present energy. eutectic mixtures used eutectic mixture of oxygen-releasing salts and the These combustible substances lowering the freezing point of these salts consist on the one hand of oxygen supplying, inorganic salts and on the other hand from the solidification point of these salts lowering combustible compounds. Its share in the total eutectic mixture is between 20 and 70% by weight, preferably between 30 and 50% by weight.

Mainly ammonium nitrate and / or sodium nitrate come into consideration as inorganic salts. but also other alkali or alkaline earth nitrates and / or

jo perchlorates can be used.

The combustible compounds include the nitrates and perchlorates of amines and derivatives of ammonia. Primary, secondary and tertiary alkyl and aryl amines (e.g.

Methylamine, ethylamine, aniline, phenylenediamine), cyclic amines (e.g. hexamethylene tetramine) or polyvalent amines can be used (e.g. ethylene diamine, hexamethylene diamine or tetraethylene pentamine).
The derivatives of ammonia include hydrazine. Urea and its substitution products, urethanes, guanidine and quaternary ammonium compounds. The ammonium salts of aliphatic carboxylic and sulfonic acids, such as, for. B.

* "> Ammonium format, ammonium acetate, ammonium sulfamate and the amides of these acids, such as formamide, acetamide, urea and its derivatives, such as urethanes, ureal and carbamic acid.
Ammonium thiocyanate, ammonium hypophosphite, ammonium thiosulfate, anhydrous sodium acetate and mono- and oligosaccharides are also suitable as combustible compounds which lower the freezing point.
Ammonium nitrate and urea in a weight ratio of 1: (0.6 to 1.5) are preferably used as the main constituents of the eutectic mixture serving as the base.

The eutectic mixtures according to the invention can also contain liquid compounds which are soluble in them

«> Are added * such as high-boiling alcohols (glycerine, Glycol, diglycol and others).

For controlling the consistency of the erfindungsgemüßcn eutcktir.chen mixtures with swelling agents can be used in amounts of 0.1 to 10 Gcw.- ⁿ / o. preferably 1 to 5

^h 'i wt .-%, are added. The swelling agents protect these mixtures or ammonium tri-nitrate explosives made therefrom both from segregation and from water wrestling. As a swelling agent

2i 26

come ζ. B. oligo- or polysaccharides are possible. Examples include: guar flour, locust bean gum, agar-agar, starch, cellulose derivatives (e.g. their esters, ethers and glycolates), proteins and gelatins, gum arabic, tragacanth and alginates.

Thickening agents such as polyacrylamides, polyacrylic acids, polyvinyl alcohol and can also be used as swelling agents Polyoxymethylene in question; Inert, finely dispersed thickeners such as bentonites and silicic acid can also be used and silicates can be used. ι ο

If appropriate, the swelling agents can also be crosslinked. By adding antibacterial agents such as z. B. salicylic acid, the swelling agents can be made durable.

To better dissolve the thickener and to liquefy the meltable components water can be added to the eutectic mixtures. In order to conserve energy it is beneficial that to keep the amount of water added as low as possible.

The eutectic mixtures according to the invention provide energy and heat when they are converted and are can therefore be used as such directly as explosives or can be used to manufacture explosives be used.

With the eutectic mixtures according to the invention, high-energy explosive mixtures with adjustable Handling safety are manufactured. There come z. B. in question explosives based on these eulectic mixtures and of:

The advantages of the erfindiingsgemäßen eutectic mixtures and of the finished explosives with them are that they at temperatures below - can be used 10 ⁰ C. Further advantages are that the energy, detonation capacity and consistency of the eutectic mixtures and the explosives produced with them can be varied within wide limits. The handling safety of these eutectic mixtures or the explosives produced with them depends on the proportion of components capable of detonation; however, it is always considerably better than that of the components capable of detonation alone.

The following examples describe and illustrate the invention. You should follow the inventive idea in no way restrict it.

example 1

The composition of the following six eutectic mixtures are according to the invention. They were produced by melting the individual components together and have the composition by weight listed in the table below. They are all ^{still liquid at - 20 °} C .; some are still liquid even at -35 ° C.

Triethanolamine nitrate 70 - - - - -
Ethanolamine nitrate - 63 32 51 56 63

30th

1. High explosives, such as pentaerythritol tetranitrate, Tetranitromethylamia, Cycictrimethylene trinitramine, to which metallic fuels such as aluminum or magnesia may be added could be.

2. Explosives based on oxygen supplying salts such as ammonium nitrate, alkali or Alkaline earth nitrates and / or perchlorates, to which explosives may be added could be.

The eutectic mixture can be produced by melting the individual components together Components or by neutralizing the mixture of amines with the corresponding acids, Dissolve the remaining components of the eutectic melt and evaporate the water. During the Neutralization, acids or bases can also be mixed with the other components, if none undesirable side reactions occur.

This can be used for the production of explosives on the basis of these liquid, eutectic mixtures eutectic mixture as such are added to the abovementioned explosive components or in the finished explosives mixture arise. 5;

The thickeners can be added to the liquid, eutectic mixture or the finished explosives mixture will.

The production of the explosives according to the invention can be carried out in the methods for conventional explosives or for «) Mud-like explosives provided equipment take place.

| Depending on the intended use, the composition and consistency of the explosives can vary with the eutectic mixture according to the invention thus varies t> s that the explosives are available in the form of cartridges or as a pump- ocltr pourable mass stand.

Methylamine nitrate

urea

Ammonium nitrate

10 - 16 17 20 10
10 27 32 17 24 27
10 10 20 15 - -

Example 2

A eutectic mixture was produced with the following composition:

Methylamine perchlorate 21% Ethanolamine nitrate 40% Methylamine nitrate 13.5%

Urea 13.5%

Ammonium nitrate 12.0%

This mixture contains more than 30% by weight of the alkanolamine or methylamine salts according to the invention; It is therefore still liquid at -20 ^0C. It also contains so much substances capable of detonation that it ^{results in a lead block bulge according to Trauzl of 250cm 3} / 10g

Example 3

The eutectic mixture according to the invention, which does not yet solidify at -20 ° C., consists of

Eutectic mixture Part < Methylamine perchlorate 16.0 Ethanolamine nitrate 45.0 Methylamine nitrate 16.0 urea 12.0 Ammonium nitrate 11.0 Guar flour 2.5

was used to produce a plastic explosive with the following composition:

30% gelled, eutectic mixture,
70% cyclotrimethylene trinitrate.

The lead block bulge according to Trauzl is 380 cm VIOg.

Example 4
An ammonium nitrate explosive with the following composition

Ammonium nitrate 49.59 j

Sodium nitrate 3.0%

Aluminum 10.0%

Hexogen 15.0% gelled, eutectic

Mixture (as in example 3) 223%

at a bulge according Trauzl 480-500 cm ^3/10 g.

Claims (5)

Patent claims: 1. Foreign energy, for the production of explosives suitable, eutectic mixture based on oxygen-releasing salts and the Combustible substances that lower the freezing point of these salts, characterized in that that there is at least 30 wt .-%, preferably 50 to 70 wt .-%, nitrates and / or Contains perchlorates of alkanolamines and has a freezing point <- 10 ° C. 2. Energieliefemdes, eutectic mixture according to claim 1, characterized in that up to 50 % By weight of the alkanolamine salts by alkylamine nitrate or perchlorate, preferably methylamine nitrate, are replaced. 3. Energieliefemdes, eutectic mixture according to claims 1 and 2, characterized in that it additionally 20 to 70% by weight, preferably 30 to 50% by weight, nitrates or perchlorates Contains ammonium and / or hydrazine and / or alkali and / or alkaline earth metals 4. High-energy, eutectic mixtures according to Claims 1 to 3, characterized in that they contain a thickener and optionally water in proportions of up to 5%. 5. Use of the eutectic mixtures according to claims 1 to 4 for the preparation of High-energy and safe to handle explosives with explosive substances and / or other oxygen-supplying salts.